Acrolein treatment of feathers



r 2,925,315; ACROLEIN TREATMENT OF-FEATHERS Varsenig Z. Pasternak, Cincinnati, Ohio, assignor to the United States of America as represented by the SecretaryoftheArmy i No Drawing. pplication April 23, 1957 Serial No. 654,617 1 11 Claims. (Cl. 894.10)

description of the method presentlypreferred by me.

In explanation of the expression .filling power,.reference may be made to'the 'repo rt entitled:A Proposed Method for Measuring the FillingPowenof Down and Feathers, by Henry A. Sinski,--publication No. TD- 103037, The Office of Technical Services, Department of Commerce, and to the article by'N. B.Edelman inTextile Research Journal, vol. 17, p.199 (April 1947 entitled lnvestigation of Methods for-Determining theFilling Power of Feathers. See also'the Sinski et al. Patent No. I

2,706,910, dated April.26, 1955. Ordinarily, chicken feathers have a filling power of 1.8 to 2.1 cm., while the 40/60 down-feather mixture has a filling powerof 5.3 to5.9cm. t A.

The term feathers as used herein includes whole land fowl feathers of the desired size range,-crushed commercial curled) land fowl feathers,lan d fowl feather fibers, stripped land fowl feathers, and mixturesof these.

In the preferred procedure,'the feathers, if not known to be entirely free fromblood, are first soaked forabout ten minutes at about 110-1-25' F. in-a water solution of a commercial blood solubilizer, su'ch asCoagusol (a mixture of sodium hexametaphosphate and alcohol sulfate). After the soaking, the solution is drained from the feathers and the feathers are then laundered'or dry cleaned. In laundering, preferably a detergentsuch'as- Tergitol NPX (alkyl phenyl ether of polyethylene glycol) is used (0.25% water solution at ll012 5 F.). Other nonionic detergents have been found to be satisfactory. In general, the non-ionic type of detergents should be used to obviate any action on the protein of the feathers.

Laundering continuesfor about twenty minutes, then the solution is removed from the feathers by centrifuging or wringing. While a number of well-known dry-cleaning solutions could be used to'clean the'feathers, laundering is preferred because it is less expensiveg' Both laundering and dry cleaning may take place in the same vessel or container thatis used during the blood solubilizingstep. Of course, if the feathers as initially received are perfectly clean, the soaking and washing or dry cleaning may be omitted.

If the feathers are from immature chickens, the damp feathers from the described laundering or dry cleaning operation are placed in a 1% water solution of trisodium phosphate Na PO .l2H O at 43 -49 C. for about ten minutes.

If feathers'from maturechickens arebeing nited 1 ..,.p.;. ...t. Feb. .16, reap 2 processed, the phosphate treatment period is increased-to about thirty minutes. This mild alkaline treatment of the feathers is believed to alter the stability of the feathers by modification of'the cystine linkages in the keratin. This step is important because it materially increases the curliness of the feathers and it curls: naturally uncurly mature feathers, therebyto increase the bulk value of the finaljfeathe'r product. Other suitably butfered alkaline solutions, for example, sodium carbonate orborax, may be used in lieu of the phosphate solution mentioned above, but in all cases the, time of the treatment must be less for immature feathers to avoid excessive degradation. Trisodium phosphate is? preferred because of I its quicker action due to a higher pH. It is believed that the higher concentration of cystine linkages inmature feathers enables them to resist the action of the alkaline solution for .a longer period. r

I now proceed tojdescribe a number of feather treatments with aqueous acrolein solutions in accordance with my invention, at temperatures of about 35-46 C. based on laboratory runs at The Tanners Council Research A 45 gram batch of chicken feathers was soaked in a sodium phosphate solution, as above described, forthirty minutes at 42+43 C. 'Then the feathers were wellrinsed with water and were placed in a 2% bath of acro-' lein (acrylaldehyde), an.unsaturated aldehyde. This bath was composed of 23.5 ml. of acrolein, 1 gram of aluminum sulfate, 1000 ml. of water and enough dilute acidto give a pH of 2-3. In lieu of aluminum sulfate, chromium acetate or ferrous ammonium sulfate may be used. The feathers remained in the bath for 45 minutes at a temperature of 3845 C. The feathers in the bath Were then exposed to sunlight for fifteen minutes at 44 0., thus making the aggregate time of immersion of the feathers in the acrolein bath about one hour up to this point. Then the pH was raised to 7 by adding dilute Na CO the bath still being exposed to sunlight for fifteen more minutes. The vessel containing the feathers. was then placed in a warm water bath in a hood and kept the-re for fifteen additional minutes, the total reaction time'being ninety minutes. Then the feathers were thoroughly rinsed, dried and cured at 87 .89 C. The filling power immediately after the cure was 62, but after aging for nine months, the filling power'was found to be 6.6 to 7.0. After laundering the treated feathers, drying in'bags and relaxing, the filling power was 6.5, a better figure than that noted ,at the conclusion 'of the run. The feathers showed definite resistance to papain digestion, which'is a good indication that they will resist microbiological attack.

HYDRAZlNE ACROLEIN TREATMENT A batch of 45 grams of chicken feathers, after the described phosphate soak and rinse, was treated with a 0.1% hydrazine solution, pH 8, at 33-35 C. for fifteen minutes, then the feathers were removed from the solution and well rinsed with water. Next the feathers were immersed in an acrolein solution of a strength slightly above 2% (26 ml. acrolein in 1000 ml. of water) at about 5.5 pH for thirty minutes at 43-.-46 C. No metallic ions were present as in the treatment described above. Then acid was added to lower the pH to 2 and the bath was maintained at 43 C. for thirty minutes. Next, in order to allow the double bond to react, the pH of the solution I "was raised to 7.5 and kept for twenty minutes at 40 C. The pH was further raised to 10-11 and the bath was warmed to 43 -46 0., this portion of the treatment continuing for thirty minutes. Then the feathers were thoroughly rinsed, dried and cured at 87 C. The filling power of these feathers was'6.2. After laundering, drying and letting them relax, the feathers still had a filling power of 6.2. Moreover, the feathers were definitely enzymeresistant.

ACROLEIN POLYMERIZATION IN SITU A batch of 67 grams of chicken feathers was given the phosphate soak described above, then was well rinsed in water. Next the damp feathers were immersed for fifteen minutes in a ferrous ammonium sulfate solution made up from 12 grams Fe(NH (SO .6H O in 1500 ml. of water. Then the feathers without rinsing were transferred to a 6% acrolein solution containing 10 ml. of 30% hydrogen peroxide. It should be noted here that the transfer without rinsing is ess ntial and the strength of the solution is important. The ferrous ion in the presence of hydrogen peroxide is oxidized to the ferric ion, which produces a hydroxyl ion and a free radical H or OH+ which initiates a polymerization. Benzoyl peroxide (benzoyl superoxide) or otI :r initiator could have been used in lieu of H 0 The feathers were kept in the acrolein bath for 180 minutes at pH 4.5 and 35-46 C., during which period they turned an apricot color. Then they were rinsed, dried and cured. Filling power, 6.2. After the treated feathers had been laundered, dried in channels (to simulate conditions in a sleeping bag) and allowed to relax, their filling power was 6.1.

The following table gives data relative to experimental acrolein treatments:

Table l SHOWING EFFECT OF TREATMENT OF CHICKEN FEATHERS \VITH ACROLEIN UNDER DIFFERENT pH Lot No.

Reaction Filling Pretreatment pH Power in cm.

Run No.

6 trisodium phosphate. do

The feathers from run No. 38 of the above table were laundered and after drying and relaxing showed an increased filling power, viz., 5.9.

Table II SHOWING EFFECT OF ACROLEIN TREATMENT ON IIIGH GRADE CHICKEN FEATHERS FROM IMMATURE CHICK- ENS (FILLING POWER 3.7 CM.)

Pretreatment Time in Minutes Filling Power in cm.

Run N 0.

Initial to Final pH Levels Reagent pH no acrolem treatment.

H thu Cn our 4 Table III SHOWING EFFECT OF ACROLEIN TREATMENT ON DRUM WASHED FEATHERS FROM IMMATURE WHITE ROCK CHICKENS (FILLING POWER 4.3 OM.)

Run Acrolein, Filling No. Metallic Salt Sol. Reaction pH Power Percent 230 Chromium Acetate 2 g... 2 9.0-2. 8-6. 6 5. 7 231 First treated with alumi- 2 9. 6-2. 8-6.6 6. 5

num sulphate, then with acrolein. 232.-- Chromium AcetateQ g... 2 9. 3-2. 9-6. 9 5. 8 233.-. Aluminum sulphate 2 g. 2 2. 8-6. 8 5. 9 234. First treated with hydra- 2 9.6-2.8-66 6.1

zine sol. then 2 g. chromium acetate. 235. Ferrous ammonium sul- 6 V 4. 5 6.2

phate plus H 01. 237 o 6 4.4 6.3 210 do 1 8 4. 5 6.1

1 Cloudy, partially polymerized before use.

The only aldehyde-treated feathers which are known to show complete resistance to pa aain-bisulphite digestion are acrolein-treated feathers, regardless of the presence of metallic ions in the acrolein treatment. This suggests that some kind of a cross-linking has taken place. Polymerization experiments were quite successful when a 6% acrolein solution was used in the presence of hydrogen peroxide after the feathers had been dipped into a 0.02 mole ferrcus ammonium sulphate solution. No apparent polymerization took place when, only 2% acrolein or 8% cloudy, partially polymerized acrolein was used. In acrolein-treated feathers, whenever a filling power of 6.1-6.5 was obtainel, the number of loose barbs was reduced. Acrolein-treated feathers'seem to improve or aging. Feathers from eleven-weeks old Arbor Acres chickens treated with a 2% acrolein solution in the presence of 1 gram of aluminum sulphate at pH 2-3 and then at 7.0, showed a filling power of 6.2 Nine months later, under adverse conditions with a relative humidity of 75-80% and a defective '(warped) piston of the Sinski filling power apparatus, the filling power of the same lot of feathers was 6.6. Thus, it is clear that acrolein, probably because it is unsaturated, gives better results than almost any other aldehyde. In this connection, reference should be made to tie copending application of Varsenig Z. Pasternak and Robert M. Lollar, Serial No. 658,900, filed concurrently herewith, now Patent No. 2,886,399, dated May 12, 1959, entitled Aldehyde Treatment of Land Fowl Feathers.

Having described my invention, I claim:

1. A method of treating land fowl feathers to enhance their filling power, which comprises modifying the cystine linkage of the keratin of said land fowl feathers by soaking said feathers in an aqueous alkaline solution, rinsing said feathers, then placing the feathers in an about 2%- 6% aqueous solution of acrolein having an initial pH of about 2-5.5 and at a temperature of about 35 -46 C., said solution containing a catalytic amount of a member of the group consisting of aluminum sulfate, chromium acetate and ferrous ammonium sulfate, then increasing the pH of the solution to about 7-11, keeping said feathers in said solution until their filling power is increased, then rinsing and drying the feathers.

2. The method according to claim 1, wherein said aqueous alkaline solution is an approximately 1% solution of trisodium phosphate.

3. The method according to claim -1, wherein said aqueous alkaline'solution is a mildly alkaline hydrazine solution.

4. The method according to claim 1, wherein said feathers are soaked, prior to said acrolein treatment,

first in an aqueous trisodium phosphate solution having their filling power, which comprises modifying the cystine 6. A method of treating land their filling'po'wer, which comprises treatingthe land fowl I featherswith anabout 0.1% hydrazinesolution of about pH 8, at about 33- 35 C. for about fifteen minutes; re-

moviug the vfeathers and rinsing them; then immersing the feathersv in anaqueo usTsolution;of acrolein of ,a a

llnkageof the keratinot said lan ing said feathers inan aqueous alkallne solution, rinsing said feathers, then placing said land fowl feathers, for] assists about one .hour in an aqueous'acro lein bath having as L temperature .above room temperature, and containing a catalytic amount of a member of the fgroup consisting of .Y

aluminum sulfate, chromium acetate, and ferrous ammonium sulfate, the pH of said bath-being about '2-3, j

thenraisingthe pH of the bath to about 7 by adding a mildly alkaline solution, exposing the "bath and the feathers therein to sunlight having a cataly'tic action for about .half an hour, partly before and'partly' after neutralizing]; the solution, and allowing thereaction'to'continue'above room temperature. untilthe fillingapower of 'the'feathers 7 is increased, in the absence ofsuch light',-then rinsing and;

drying said feathers.

fowl feathers toenhance ifeathers and: drying 7 them.

l feathers by soalr-f 15, minutes in a 'ferrous a mmonium sulfatesolutiomthe yferrous ammonium sulfate contents 1 of said solution being of-suflicient strengthto exert a catalytic efiect during the subsequent acrolein. treatment; then without rinsing the feathers transferring them to an about 6% aqueous acroleinsolution containinga catalytic amount of a n m oxidizing peroxide catalyst, whereby. said acrolein is; at z 'leastpartly polymerized in situ, andkeepingthefeathersv 'in thebath for about 180 minutes at a pH offabout' 4.5 i' 4 -46, C.; then rinsing the and {a temperature of about 35 gsrn 'rfnethod ,of' treating ira fowl feathers: with q I ."afcrolei n to venhance their filling powenfwhich comprises v 1" immersing the land ,fowl feathers,{.-prior to the acrolein sulfate, solution, the. ferrous'ammonium'sulfate contents v offsaid.'solutioubeing of s'uflicientstrength to exert a treatment,- for about l5 minutes ina ferrous ammonium catalytic effect during the subsequent acrolein treatment;

- then without rius'ing' the'ieathers transferring ,themto an strength slightly above 2% at pH aboutI5.5;for]about-} V 7. A method of treating land fowl feathers y acrolein to enhance their filling power, which comprises;

flmodifying the cystine linkage of the keratin of saidlandfowl feathers by soaking',said'- feathers-man aqueous alkaline solution, rinsing said feathers; then immersing S,

the feathers, prior to the acrolein treatment, for about about; aqueouslac'rolein' solution containing a cat'a lytic amountof an oxidizing peroxidecatalyst, whereby said] acroleinlfis at least partly polymerized in situ, and

kee pin g thefeathers in thebath for about-180 minutes at *a pH of abjout 4.5?and atemperature of about 3546 0.; ,then'rinsi'ng the feathers sand drying them,"

I 9.=The product produced by the method of claiiml 5 g Q 7 1O. The product producedby' the method-ofclaimo 111. The product producedhy the methodfof c1aim8f'i UNrrE STAT-ES, PATENTS, v

2,805,914 Frederick Sept. 10, 1957 ReferencesjCitedinthe file'of this fastest; i 

7. A METHOD OF TREATING LAND FOWL FEATHERS WITH ACROLEIN TO ENHANCE THEIR FILLING POWER, WHICH COMPRISES MODIFYING THE CYSTINE LINKAGE OF THE KERATIN OF SAID LAND FOWL FEATHERS BY SOAKING SAILD FEATHERS IN AN AQUEOUS ALKALINE SOLUTION, RINSING SAID FEATHERS, THEN IMMERSING THE FEATHERS, PRIOR TO THE ACROLEIN TREATMENT, FOR ABOUT 15 MINUTES IN A FERROUS AMMONIUM SULFATE SOLUTION, THE FERROUS AMMONIUM SULFATE CONTENTS OF SAID SOLUTION BEING OF SUFFICIENT STRENGTH TO EXERT A CATALYTIC EFFECT DURING THE SUBSEQUENT ACROLEIN TREATMENT, THEN WITHOUT RINSING THE FEATHERS TRANSFERRING THEM TO AN ABOUT 6% AQUEOUS ACROLEIN SOLUTION CONTAINING A CATALYTIC AMOUNT OF AN OXIDIZING PEROXIDE CATALYST, WHEREBY SAID ACROLEIN IS AT LEAST PARTLY POLYMERIZED IN SITU, AND KEEPING THE FEATHERS IN THE BATH FOR ABOUT 180 MINUTES AT A PH OF ABOUT 4.5 AND A TEMPERATURE OF ABOUT 35*-46*C., THEN RINSING THE FEATHERS AND DRYING THEM. 